Chrome disazo dye



Patented Feb. 22,1944

CHROME msAzo- DYE "Boyce G. Carson, Woodstown, N. J., assignor to E91. du Pont de'Nemours & Company, Wilmington, Del 'a corporation of Delaware No llrawinga, Application May 29, 1941,

r. a Serial No. 395,734

lClaim's. (Cl. 260-147) This invention relates to new soluble chromable ,disazo dyes which are especially suitable for dyeing wool and similar dyes-ble fibers.

In the dyeing of olive drab shades on wool. mixtures of chromable wool dyes or various shades are commonly used, one of which gives dyeings primarily in shades of yellow to brown. Heretofore, there has not been available such a dye which has a satisfactory combination of properties which are needed for "such dyeings, such as good light IastneS-S good. carbonizin iastness and good fastness to severe washing and fulling. It was therefore desirable to provide dyes for the indicated purposes which have the desired 1 combination of properties and which are made 5 from readily available intermediates.

It is among the objects of the present invention to provide soluble chromable disazo dyes which dye wool and similar d-yeable fibers in fast shades.

Another object of the invention is to provide for making fast chromed dyeings on wool-and similar dyeable fibers in various shades such as yellow, brown and red. Another object of the invention is to provide chromed dyes which have good fastness to light, washing, fulling and carbonizing.

Other objects of the invention will be apparent from the following description. l

The objects of the invention are attained by providing disazo dyes which are represented by the general formula wherein R. is an aryl group containing in the ortho position to the azo bridge one of a lake iorming group consisting of carboxy,

-..CH2 CO0H;' wherein the aryl nucleus is one of a group consisting of the benzene and naphthalene series which is substituted by one of a group consisting of phenyl and Y) wherein Yis. from a roup consisting 4d of hydrogen, alkyl having 1 to 4 carbonathe corm responding alkoxy groups; chloro, bromo, nitro, SOaH and--C0.0,H and n is an integer not greater than 2; Pyis the residue of one'of a group consisting of amino-aryl -pyrazolones and sulroamino-aryl-pyrazolones of the phenylene and naphthalene series in which the 3-position ofthe pyrazolone group is substituted by one of :agroup consisting of methy ph nvl and COQ M wherein M is one of agrollp onsist-i 3 0f hydroge methyliand ethyl; and R" is salicylic acid;

The dyes are made by dia'zotizing any of the above indicated mono-amino aryl compounds of the benzene or naphthalene vseries which have a carboxy, S-CHz--COOH or -O-CH2-COOH group ortho to the primary amino group, and coupling with a pyrazolone of the group consist- .ing of the amino-aryl-pyrazolones and sulfoamino-aryl-pyrazolones of the phenylene and naphthalene series in which the 3-position of the pyrazolone nucleus is substituted by methyl, phenyl, carboxy, methyl ester or ethyl ester grou The amino-substituted monazo compound thus obtained is then diazotized and coupled with any azo dye coupling component of the phenolic type which is devoid of primary amino groups. The resulting disazo dye is then separated from the couplingmedium, as by salting' and filtering out the precipitated product.

The disazo compounds thus produced are soluble in water and they produce direct dyeings on wool from hydrous solutions inyellowish shades.

Upon chroming the dyeings by methods well known in the art, dyeings having good fastness properties in somewhat darker yellowish to reddish shades are produced. Instead of dy ing y the afterchrome process, equally good results are obtainable by applying the dyes in accordance with metachrome methods.

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and not aslimitations thereof. Parts are expressed in parts by weight unless otherwise noted.

EXAMPLE 1 Anthranilic acid (137.4 parts) is added to 1 liter of water and 9.1.2 parts of hydr gen Chloride The temperature of the 'jmixture is 'ilowered to 0-5 C. by the addition of ice; and sodium nitrite parts dissolved in 300 parts of water) is added with rapid stirring. After diazotization is complete, a small amount of urea or sulfamic acid is added until the small excess of nitrous acid is destroyed. The dia'zotized solution is added slowly to a mixture of 192.5 parts of 1-(3'-aminophenyl) -3-methy1-5-pyrazolone and 265 parts of soda ash in 4000 parts'of water at 0-5. Coupling proceeds rapidly, and after it is complete the free amino group of the phenyl nucleus is diazotized by adding to the solution 182.4 parts of hydrogen chloride, followed by 70 parts of sodium nitrite dissolved in 300 parts of water. The second diazotization is preferably carried out at room temperature (20-25 C.). When the diazotization is the procedure of Example 1, a yellow dye is obtained which has properties very similar to those of the dye obtained in Example 1.

The compound is represented by the formula complete, the diazo solution is added slowly to a C001; solution of 152 parts of salicylic acid and 100 l parts of caustic soda in 3000 parts of water at 0-5 C. When the coupling is complete, the dye N is isolated from the cold solution by the addition of common salt, filtering, and drying. It dyes N wool by the afterchrome or metachrome method a yellow shade having good fastness to light and excellent fastness to carbonizing, to fulling and to severe Washing. Its properties make it especially I 0H suitable for use in mixtures for dyeing olive drab l5 shades. 00011 Th compound is represented by the formula Dyeings on wool with the dyes of Examples 1 COOH i to. 3 are surprisingly resistant to color change duringcarbonizing. In the following Table I are shown other illus- ,trative' examples of the invention which were 110-0 N made 1n general by processes s1m1lar to the foregoing examples. Table I shows the components u used in making the dyes, the shades of the div rect dyeings on wool and the shades of the V Y chromed dyeings. Excellent dyein-gs on wool havr OH ing fastness properties similar to those of the foregoing examples can be made either by the k 0011 t h it n u 1 7 y me ac rome ora erc rome process.

Table I I v Direct Chromed No. Diazo component Middle couplmg component End couphng component color on color (1m W0 WOO 5-chloro-2 amino-benzoic acid 1-(3'-aminophenyl)-3-methyl-5- alicylic acid; Yellow Yellow.

pyrazolone. fi-ehloro-Z-amino-benzoic acid do Do. Amino-terephthalic acid -do D0. Anthranilic acid 1-(4'-amm0phenyl)-3-methyl-5- Do.

pyrazolone. do o 2,3 cresptinic acid DD, 5-ch1or0-2-amino-benz0ic acid. d0 n licylic acid do Do, 5-suJio-2-amino-benzoic acid 1-(3' -am1in0pl1eny1)-3- ethY1-5- 0 do Do.

' YI'&Z0 0H6. I Anthranilic acid 1-(3'-aminophenyl)5-pyraz0l0ned0 .L do Do.

3-carlboxylic acid. N-(3-carboxy-4'-aminobenzene- 1-(3-aminophenyl)-3-methy1-5- "moo do Do.

sullonyl) anthranilic acid. pyrazolone. do 1-(3'-aminophenyl)-5-pyraz0lone- 13 li -carhoxylic acid.

' EXAMPLE 2 By using an equivalent amount of aminophthalic acid instead of anthranilic acid in the procedure of Example 1, a very similar yellow chromable dye is obtained which has similar fastness properties when applied to wool by the usual afterchrome or meta/chrome methods.

The compound is represented by the formula By using an equivalent amount of 1-(3'-'-amin'ophenyl) -5-pyra zolone-3-carboxylic acid instead sisting of Primary arylamines ofthe benzene and naphthalene series having the above indicated lakeforming groups ortho to the primary amino group which are represented by the formula Y Ar%l-NH are used as the first components in making the new dyes. In this formula Z is one of the group con- --COOH, OCH2COOH and S-CHzCOiDI-I :whichis inv an orthoposition to the primary amino group; aryl is a benzene or naphthalene nucleus; and Y is phenyl or one to two members of a group consisting of hydrogen, alkyl having 1 to 4 carbons, the corresponding alkoxy groups, nitro, chloro, bromo, --SO3H and -COOI-l.

As representative of the many primary arylamines of the benzene and naphthalene series which may be used as first components to make the new dyes are mentioned anthranilic acid,

of 1-(3'-aminophenyl)-3-methyl-5 pyrazolonein 3-chloro-anthranilic acid, 4-echloro-anthranilic .anthranilic iacid, S-nitro-anthraniIic acid, 4-bromo-anthranilic' acid, -bromo-anthrani1ic acid, 6bromoanthranilic acid, 3,5-dichloro-anthranilic acid,

3,5-dibromo anthrani1ic acid, Z-amino-isophthalic acid, 2-aminophenoxy acetic acid, 2-aminothiophenoxy acetic acid, 2amino-5-.-ethoxy-thiophenoxy acetic acid, 2-amino-5-chloro-thiophenoxy acetic acid, l-amino-Z-naphthoxy-acetic acid, 1-.amino-2-thionaphthoxy acetic acid, 2- amino-3-naphthoic acid, and similar aryl amines containing ortho lake-forming groups.

The first components are diazotized and coupled with one of the above described amino substituted aryl-pyrazolones. Representative members of the pyrazolones which are suitable as second components for making the dyes of the invention are 1-(3'-aminophenyl)-3-methy1-5-pyrazolone, l- (4'-aminophenyl) -3-methyl-5-pyrazclone, 1- (3-aminopheny1) -5-pyrazolone-3-carboxylic acid, l-(3-aminopheny1)-5-pyrazolone- 3-carboxylic-methyl ester (or ethyl ester), 1-(4'- aminophenyl) -5-pyrazolone-3-carboxylic acid, 1- (4'-aminopheny1) 5 pyrazolone 3 carboxylic methyl (or ethyl) ester, 1-(3-aminophenyl)-3- pheny1-5-pyrazolone, 1-(4' aminophenyl) 3 phenyl-5-pyrazolone, 1- (4'-amino-6'-sulfo-naphthyl-l) -3-methyl-5-pyrazolone, 1- (4'-amino-6' sulfo-naphthyl-I 5 pyrazolone 8 carboxylic acid (or methyl or ethyl ester), 1-(4-amino-7- sulfo-naphthyl-l) -3-methyl-5-pyrazolone and 1- (4'-amino-'7'-su1fo-naphthyl-l) -5-pyrazolone-3- carboxylic acid (or methyl or ethyl ester).

The amino-substituted monazo compound resulting from the coupling of the first and second components is diazotized and coupled with salicylic acid.

The disazo combinations made in accordance with the foregoing description give chromed dyeings on wool of good light fastness, but the light fastness is slightly less than that of the chromed monazo dyes of corresponding shade that have the best light fastness. However, the monazo dyes of the best light fastness are in general not entirely satisfactory in respect to some other fastness property, such as severe washing, fulling or carbonizing. They are so fast to light that when fading occurs in a dyeing such as an olive drab wherein a yellow is used with dyes of other shade, the dyeing fades off-shade, in general toward the yellow. The dyes of the present invention provide dyeings having a better combination of all fastness properties than the monazo dyes. In a dye having the excellent combination of other fastness properties, it is desirable to have slightly less light fastness than that of the most light fast monazo dyes in order that the dyeings will fade on shade when fading occurs. In general the new dyes have good fastness to carbonizing and washing, and the fastness to carbonizing and washing of some members of the type is superior. Many of the new dyes withstand the most severe fulling tests and all of them are satisfactory.

From the foregoing disclosure it will be recognized that the invention is susceptible of modification without departing from the spirit and scope thereof and it is to be understood that the invention is not restricted to th specific illustrations thereof herein set forth.

I claim:

11. A chromable idisa'zo dye which-in theform of its acid is represented by the formula R- N=N-. :H;o-X 1 HO-0 N COOH ,wherein R is an aryl nucleus containing in the ortho position to the azo bridge one of a lake-formin group consisting of carboxy, SCH2COOH, -OCH2COOH, wherein the aryl nucleus is one of a group consisting of the benzene and naphthalene series which is substituted by one of a group consisting of phenyl and (Yb: wherein Y is from a group consisting of hydrogen, alkyl having 1 to 4 carbons, the corresponding alkoxy groups, chloro, bromo, nitro, -S03H and -COOH and n is an integer not greater than 2; and X is one of a group consisting of methyl, phenyl and -COOM wherein M is one of a group consisting of hydrogen, methyl and ethyl.

2. The disazo dye which in its acid form is represented by the formula (IJOOH 3. The disazo dye which in its'acid form is represented by the formula CIZOOH 4. The disazo dye which in its acid form is represented by the formula CIZOOH OOOH ortho' to the'aminogroupioi the class-consisting of carboxy, v

s cH=-cooH, O-CHz"-COOH and in which aryl is one of a group consisting of the benzene and naphthalene series which is substituted by one of a group consisting of phenyl and --(Y)1 wherein Y is one of a group consisting of hydrogen, alkyl having 1 to 4 carbons, th'e corresponding alkoxy groups, chloro, bromo, nitro, SO3H and --COOI-I, and n is an integer not greater than 2; coupling with a compound of a group consisting of amino-arylpyrazolones and sulfo-amino-aryl-pyrazolones of the benzene and .naphthalenenseries in which the 3position 'of thepyrazolonegroup is substituted by one of-a group consistingof methyl, 'phenyl and -COOM wherein M is one of a group consisting of hydrogen, methyl and ethyl;

diazotizing the resulting monazorcompound and .then coupling with salicylic acid. 7

wherein the first coupling is made with 1-(3- aminophenyl)-5-pyrazolone-3-carboxylic acid. BOYCE G. CARSON. 

